Sizing paper with either sulfone, sulfoxide or sulfide and a polyalkyleneimine

ABSTRACT

A COMBINATION OF A 2-CHLROALKYL SULFONE, A 2-CHLOROALKYL SULFOXIDE OR A 2-CHLOROALKYLSULFIDE, AND A POLYALKYLENEIMINE WHICH IS USEFUL AS A SIZING AGENT IN THE PREPARATION OF SIZED CELLULOSIC PAPER SUBSTRATES.

United States Patent 3 576 712 SIZING PAPER WITH EITHER SULFONE, SULF- OXIDE 0R SULFIDE AND A POLYALKYLENE- IMINE William Robert Hine, Jr., Kirkwood, and Myron J. 'Holm, St. Louis, Mo., assignors to Monsanto Company, St. Louis, M0.

N0 Drawing. Continuation-impart of abandoned application Ser. No. 520,639, Jan. 14, 1966. This application Apr. 16, 1969, Ser. No. 816,772

Int. Cl. D21h 3/40; D21d 3/0 U.S. Cl. 162-168 8 Claims ABSTRACT OF THE DISCLOSURE A combination of a 2-chloroalkyl sulfone, a 2-chloroalkyl sulfoxide or a 2-chloroalkylsulfide, and a polyalkyleneimine which is useful as a sizing agent in the preparation of sized cellulosic paper substrates.

This application is a continuation-in-part of application Ser. No. 520,639, filed Jan. 14, 1966, and now abandoned.

This invention relates to the sizing of cellulose paper substrates. More particularly this invention provides new combinations of materials which are very efiective as sizing agents under acid, neutral and alkaline pH conditions to give permanent sizing under conditions which are compatible with present papermaking procedures.

An object of this invention is to provide a combination of chemical ingredients which will size paper under a variety of pH conditions to give permanent sizing while being compatible with present papermaking procedures.

Briefly, it has been found that fibrous materials, particularly fibers of cellulose and the like, may be sized by applying to the fibrous material a combination of (a) a compound of the formula R-S (O)nOHz( 3H-R where R is any organic hydrocarbon hydrophobic group, and R is hydrogen, methyl, or chloromethyl and n is an integer of from 0 to 2 (b) a polyalkyleneimine having from 2 to 3 carbon atoms in each alkylene group, and thereafter drying the thus treated fibrous material. This combination of the 2-chloroalkyl sulfone, sulfoxide, or sulfide, and the polyalkyleneimine may be applied by any convenient method known to those skilled in the sizing art. They may be combined in one solution or dispersion and added to an aqueous fibrous slurry or pulp slurry, or they may be sprayed on to a fibrous mat or paper web. They may also be applied by tub sizing methods by passing cellulose containing webs or textiles through solutions of the combined ingredients or through separate solutions of the two ingredients to effect contact of the cellulosic fiber material with both of the 2-chloroalkylsulfur compound and the polyalkyleneimine. Generally, the combination of the 2-chloroalkyl sulfone, sulfoxide or sulfide, and the polyethyleneimine is applied in combined amounts of the two ingredients sufficient to impart from about 0.01 to about 5% or more of the weight of the dry cellulose fibers.

A preferred example of the application is to add to the aqueous pulp slurry used to make cellulose containing paper, either separately or in combination a higher alkyl 2-chloroethyl or 2,3-dichloropropyl sulfone and a polyethyleneimine, the combined amounts of the two ingredients being between about 0.1 percent to about 5.0 percent of the weight of the dry pulp fiber in the pulp slurry being treated, although total percentage amounts may range from about 0.1 percent to any higher amount dicf 3,576,712 Patented Apr. 27, 1971 tated only by cost. The two ingredients are preferably combined in weight ratios of about 1:1 to 1:3 of the 2-chloroalkyl hydrophobic sulfone; polyethyleneimine although suitable weight ratio proportions may range from about 1:10 to about 10:1 and still get a sizing efiect. A minimum of about 0.2% of each component should be used for effective sizing. The 2-bromoalkyl sulfides, sulfoxides and sulfones could also be used, if desired.

In another preferred aspect of this invention the sizing agents may be applied as a surface size to previously formed, untreated fibrous mats or cellulose containing -webs. The combined amounts of the two aforementioned ingredients in this aspect of the invention are generally between 0.02% to about 5.0% of the weight of the dry cellulose fibers. However, higher concentrations of the ingredients may be applied if desired, but for most practical purposes, higher concentrations are generally not needed. In this aspect of the invention the two ingredients are preferably combined in weight ratios of about 1:1 to 1:3 of the 2-chloroalkyl hydrophobic sulfone; polyethyleneimine although suitable weight ratio proportions may range from about 1:10 to about 10:1 and still attain a sizing effect. The 2-bomoalkyl sulfides, sulfoxides and sulfones could also be used in this aspect of the invention.

The effect of this particular combination of a 2-chloroalkyl sulfone, sulfoxide, and sulfide and a polyalkyleneimine is quite unexpected because combination of related materials such as 2-hydroxyethyl octadecyl sulfone with polyethyleneimine and applied in a manner similar to the application of Z-chloroethyl octadecyl sulfone and polyethyleneimine gave essentially no sizing. However, we have found that 2,3-dichloropropyl hydrophobic hydrocarbon sulfides and sulfoxides can be used to effect sizing in accordance with this invention or to replace a part or all of the corresponding sulfone in the sizing combination but the sulfone is preferred because it is more effective in this combination. The 2,3-dichloropropyl hydro phobic sulfide is much more effective in this sizing combination than is the 2-chloroethyl hydrophobic sulfide. When the 2-chloroalkyl sulfides and sulfoxides are used, however, it is usually necessary to cure the treated cellulosic material, e.g., at C. for 1 hour, to effect the sizing. The corresponding sulfones in this combination effect sizing without a prolonged curing step and hence the sulfones are preferred.

The 2-chloroalkyl hydrophobic sulfides, sulfoxides, and sulfones which we have found to be useful for sizing fibrous materials, particularly cellulosic fibrous materials include those in which the hydrophobic group is a higher alkyl having at least about 10 carbon atoms, e.g., decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, tetracosyl, and pentacosyl and higher alkyl up to about 40 carbon atoms if desired, although those having up to about 25 carbon atoms are preferred, the corresponding alkenyl groups having from 10 to about 40 carbon atoms, a few examples of which are decenyl, tridecenyl, heptadecenyl, octadecenyl, eicosenyl, tricosenyl, etc., the alkylphenyl and alkyl-substituted cycloalkyl having at least about 8 carbon atoms in the alkyl groups attached to the phenyl or cycloalkyl group, e.g., octylphenyl, dinonylphenyl, dodecylphenyl, tridecylphenyl, pentadecylphenyl, octadecylphenyl, heneicosylphenyl, nonylcyclopropyl, dodecylcyclobutyl, tridecylcyclopentyl, tetradecylcyclohexyl, pentadecylcycloheptyl, octadecylcyclohexyl, etc., and any of such alkyl, alkenyl, alkylphenyl and alkylcycloalkyl, 2-chlor0alkyl sulfide, sulfoxide, or sulfone compounds containing non-interfering inert substituents. Inert substituents which may be present include groups such as carboalkoxy, alkyloxy, aryloxy, arylalkyloxy, keto(carbonyl), tertiary amide, halogen attached to aromatic carbons, or aliphatic heterocyclic groups, i.e., heterocyclic radicals containing no benzene-type unsaturation. The heterocyclic radical may be saturated or unsaturated. Types of radicals which should not be present to any substantial extent in the hydrophobic group are exemplified by hydroxyl groups,

4 The combination of the sizing ingredients of this invention may also be used in conjunction with starches such as Stayco A, an oxidized corn starch by A. E. Staley Mfg. Co., when the sizing ingredients are applied to the cellulosic fibers by surface sizing techniques.

primary and secondary amino groups, labile halogens, 5 The polyalkyleneimines used in this invention are the amide groups having amido hydrogen, and carboxyl or polymerization products of ethyleneimine or derivatives other acidic groups. Those skilled in the art will be aware hereof. Those used in this invention are those havin of the types of hydrophobic groups which may be used from 2 to 3 carbon atoms in each alkylene group which in these 2-chloroalkyl sulfide, sulfoxides, and sulfone comare water soluble. Such products are described, for exampounds if undesired side reactions are to be avoided. pl i US. Pat- 2,192,306. The poly(N-methylalkylene- These sulfide, sulfoxide and sulfone compounds can be imines) which may also be used are the polymerization used as single pure compounds for the purpose of this Products of N'methyl'ethyleneiminea y -p Py invention. However, in commercial practice, 2-chloroimine, miXtllreS ereofalkyl sulfide, sulfoxide and sulfone compounds containing, The following examples will further illustrate the nature e.g., mixed hydrophobic alkyl, mixed alkenyl and alkyl, of the invention but the invention is not intended to be alkylphenyl, or alkyl, and alkyl-substituted cycloalkyl icted theretO- groups may conveniently be used. Mixtures of sulfides, LE 1 sulfoxldes and l e are also useful This example illustrates the substantially enhanced For some apphcatlons of these eombmatlons of mate sizing eflFectiveness obtained by using the combination of rials to some cellulosic fibrous materials, increased sizing polyethyleneimine and a 2 ch1oroethy1 sulfone of the effectiveness 15 noted when these 2-chloroalkyl sulfide, type provided for by this invention as compared to a sulfoxide and sulfones are applied to the fibrous substrate hydroxy ethyl sulfone. admixed with or simultaneously with a basic material such For this example, polyethyleneimine was added to a as an alkalnmetal hydrox 1de 1n an amount sufficient to 2% paper pulp slurry in Water in amount to equal 1% efiect the sizing on the basic side of the pH range, that is, based on the dry Weight of the pulp in the slurry, stirred l f PH 7 elther pnor to slmultaneouely Wlth the for 15 minutes, and then 1% based on the Weight of the eddmon of the polyethylenelmme- When 'f proeedllre pulp, of either 2-hydroxyethyl octadecyl sulfone as a 15 eontemPleted the base W111 k be Sodlum hydroxlde solution in xylene or 2-chloroethyl octadecyl sulfone as a beeePse 1t 15 most readlly avelleble and the most solution in p-cymene was added which were emulsified nornical one to use. However, it is understood that other in Water using hexadecyltrimethyl ammonium bromide g ezig igf ii zi gg fig gz g g ik l i (rarquad) as an emulsifying agent. After stirring to obs y 1 an er a a 1 meta ta1n umform dispersion, the treated pulp was formed into and alkahne earth metal bases and basic salts could be paper Sheets on a Noble and Wood paper making used If e chine. The paper sheets obtained were dried and some e eombmatlen of the f sulfoxlde and sulfone sheets were cured for 1 hour at 105 C. and tested for afgl l s si gs zg g g igggi' zegg i e gi h?251 12251383 sizing effectiveness using the ink penetration test method tional manner. The fibrous material in the form of cellu- 32 g i of tlmihbefore mk ls Deb-served on the lipper losic pulp finished paper sheets or paper board or paper 40 V6 Sur ace as 6 measure slzmg' some fimshed paper sheets were left unwashed while others were soaked produchtextlle fi e dm or tabrw y be s p y in chloroform, dried and then tested for sizing in the PP mm a 113 6 organic solvent solution of same manner. The results of the tests are summarized in the 2-ch1oroalkyl sulfide, sulfoxide, or sulfone, and then the following table.

Cured Sizing (see) Agent used iiiige iii io i h i Unwashed Washed A {Po1yethy1eneimine 1 No 0 0 2l lggxgylgsll%gegadecyl sulfone i es 9 0 "'{2-ehloroethyl Madurai-5561:1313: 1 YZS'IIT. ?;833i ?;333i C- Polyethyleneimine 1 {gig- 2 0 into a solution of the polyethyleneimine and then dried in EXAMPLE 2 any convenient manner. The term drying and its various T adjective, verb, and Particle forms, are used herein to f o 2? aqueous slurry contalmng 2 Percent by Welght include curing of the treated fibrous substrate to give a 3 i g Gatmeau sulfite Pulp refined to a finished sized fibrous product. The amount of the 2-chloro- {an i? i Freeness of about 500:.20 and alkyl sulfide, sulfoxide, or sulfone and the polyethyleneo there was adfied an emulsion Prepared imine retained by the fibrous substrate can be controlled SS0 of z3'dlchloropropyl fq q by the concentration of the treating solution and the 6 1 SH 5 of Xylene.and mlxmg Wlth degree of squeezing or pressing of the dipped fibrous mah e tmg Solutlon 20 of a soluponpf Percent terial before drying. exadecyltnmethyl ammonium bromide in water. The This invention also contemplates the use of this combiireated aqueous P shiny was mlxed for 15 mmutes to nation of sizing ingredients in conjunction with agents ngsure umform dlstnbutlon and then i to i paper designed to increase retention of the sizing agents on the Sheets on a Noble and 00d paper makmg e l some fibrous substrate such as cellulosic fibers. Useful auxiliary s eats were merely dried and.then tested for Slzmg' other agents of this type include cationic starch, a good example sheets were cured for .60 mmutes at and then of which is a modified corn starch having a nitrogen contested tent of about 025 Percent Sold under the trade name Other batches of the same bleached Gatineau sulfite Cato =8 by National Starch Products Company. When Pulp Slurry at PH 9 were treated first with an aqueous from 0.1% to about 0.5% by weight, based on the weight Slurry of a polyethyleneimine, miXed as f e, and with of the fibrous substrate, e.g., cellulose pulp, of a cationic one of the 2,3-diCh10mPT0PY1 Il-octadficyl Sulfide Sulstarch, such as Cato 8 is added to the stock slurry before, f n emulsions, as above The resulting treated P p were after, or simultaneously with the sizing agent, a decided 7 formed into sheets as above, and either dried or cured at improvement in retention of the sizing agent is obtained.

C. for 60 minutes as above, and then tested for sizing efiectiveness by the ink test method. Some samples were washed with acetone, dried, and then tested to determine permanency of sizing. The results of these tests on the various papers is summarized in the following table.

6 What is claimed is: 1. A fibrous product comprising cellulose fibers having distributed on their surface (a) a compound of the formula Cured Amount, 1 hour/ Sizing (sec) 1 6,000+ means that the test was concluded at 6,000 seconds and is indicative of hard sizing.

EXAMPLE 3 This example illustrates the enhanced sizing effectiveness obtained by using the combination of polyethyleneimine and a 2-chloroethyl sulfone as a surface size.

Unsized paper preparation Equal parts by Weight of bleached softwood kraft pulp and bleached hardwood kraft pulp were slurried and refined to a Canadian Standard Freeness of 375. No pulp additives were used. The pH of the slurry was adjusted to 7.0 and the pulp was sheeted and dried on a Fourdrinier paper machine. The resulting unsized sheets had a basic weight 44 lbs./ 3300 sq. ft. and a Gurley porosity of 10 seconds.

2-chloroethyl sulfone emulsion preparation Cato 8 cationic starch (National Starch Co.) in an amount of 4.5 grams and 0.34 gram of sodium lignosulfonate are mixed with 150 ml. of water and cooked at 90 to 95 C. for about 15 minutes. The mixture is then placed in a Waring Blendor and 9.0 grams of 2-chloroethyl n-octadecyl sulfone is added with slow agitation and the mixture is held at a temperature of about 85 C. The resulting mixture is agitated with full speed on the blender for about minutes. The resulting emulsion is poured over 100 grams of ice and then further adjusted to 300 grams with the addition of more ice. The resulting emulsion contains 3.0 of the 2-chloroethyl n-octadecyl sulfone.

Size press solution preparation A 10% slurry of Stayco A (an oxidized corn starch of A. E. Staley Mfg. Co.) is cooked for about minutes at 90 to 95 C. diluted to form a 6% solution and cooled to room temperature.

A series of size press solutions Were prepared using in each solution 100 grams of the Stayco A solution and sufiicient amounts of the sulfone stock solution and 1% polyethyleneimine solution to provide the desired final concentration of sizing compositions on each sheet based on the dry weight of the fibers as shown in the table below.

The sheets were dipped into the size press solutions and run between the rolls of a wringer and dried on a drier at 204 F. for about 30 seconds.

Results of the sizing tests on the various papers is summarized below.

Sizing Composition on Sheet wherein R is an organic hydrophobic hydrocarbon group, R is selected from the group consisting of hydrogen, methyl, and chloromethyl, and n is an integer of from 0 to 2, and (b) a polyalkyleneimine having from 2 to 3 carbon atoms in the alkylene groups, the combined amounts of (a) and (b) being about 0.01% to about 5% of the weight of the dry cellulose fibers, and the weight proportions of (a) to (b) being from about 1:10 to 10:1.

2. A fibrous product as described in claim 1 wherein the cellulose fibers are the type used to make paper webs, the compound (a) is one in which R is an alkyl group having at least 10 carbon atoms, R' is hydrogen, and n is 2, and (b) is polyethyleneimine.

3. A fibrous product as described in claim 2 wherein the compound (a) is 2-chloroethyl octadecyl sulfone.

4. A fibrous product as described in claim 1 wherein the cellulose fibers are the type used to make paper webs, the compound (a) is one in which R is an alkyl group having at least 10 carbon atoms, R is chloromethyl, and n is 2, and the polyalkyleneimine (b) is polyethyleneumne.

5. A fibrous product as described in claim 4 wherein the compound (a) is 2,3-dichloropropyl octadecyl sulfone, and the compound (b) is polyethyleneimine.

6. -A method of preparing a treated fibrous product of cellulosic fibers which comprises applying to the cellulosic fibrous product (a) a compound of the formula wherein R is an organic hydrophobic hydrocarbon group, R is selected from the group consisting of hydrogen, methyl, and chloromethyl, and n is an integer of from 0 2, and (b) a polyalkyleneimine having from 2 to 3 carbon atoms in each alkylene group, the combined amounts of (a) and (b) being about 0.01% to about 5% of the weight of the dry cellulose fibers, and the weight proportions of (a) to (b) being from about 1:10 to about .1021, and drying the thus treated cellulose fibrous product.

7. A :method as described in claim 6 wherein an aqueous cellulose pulp dispersion is treated with an emulsion of compound (a) in which R is an alkyl group having at least 10 carbon atoms, R is hydrogen, and n is 2, and (b) an aqueous dispersion of polyethyleneimine.

8. A method as described in claim 6 wherein an aqueous cellulose pulp dispersion is treated with an emulsion 7 of compound (a) in which R is an alkyl group having at 3,310,460 3/1967 Goldstein et a1 1621 64 least 10 carbon atoms, R is chloromethyl, and n is 2, and 3,345,251 10/ 1967 Gaertner 162-158 an aqueous dispersion of polyethyleneimine.

S. LEON BASHORE, Primary Examiner References Cited 5 F. FREI, Assistant Examiner UNITED STATES PATENTS 2,961,367 11/1960 Weisgerber 162-168X 3,016,325 1/1962 Pattilloch 162168X 8116; 117-155; 162-182 

